Can an adjacent stereocenter control selectivity in the palladium‐catalyzed allylic substitution reaction? If the intermediate π‐allyl palladium complex can undergo rapid inversion, the answer is yes (see reaction scheme). Starting from chiral 5‐vinyloxazolidinones, trapping of intermediates 1 and 2, which are in a dynamic equilibrium, with nitrogen‐containing nucleophiles leads to the quantitative formation of diamines as single diastereomers.
Steuerung der Selektivität durch ein benachbartes Stereozentrum bei der Pd0‐katalysierten Substitutionsreaktion an der Allylgruppe? Ja, wenn der intermediär gebildete π‐Allylpalladiumkomplex eine schnelle Inversion eingehen kann (siehe Schema). Das Abfangen der in einem dynamischen Gleichgewicht stehenden Intermediate 1 und 2 mit Stickstoff‐Nucleophilen führt ausgehend von chiralen 5‐Vinyloxazolidinonen zur quantitativen Bildung von diastereomerenreinen Diaminen.
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